Herbicide based on cyanoalkylaminotriazines

ABSTRACT

A herbicide in which the active agent is a substituted striazine of the formula:   WHEREIN X is halogen, alkoxy or alkylmercapto, alkyl in alkoxy and alkylmercapto having one to six carbon atoms; R1 is   WHEREIN N AND M ARE ZERO OR 1 WITH THE PROVISION THAT ONLY ONE OF N AND M MAY BE ZERO; R3 and R4 are the same or different and are straight-chain or branched-chain alkyl having from one to four carbon atoms and wherein either R3 or R4 may also be hydrogen; and R2 is   WHEREIN R5 is hydrogen or straight-chain or branched-chain lower alkyl. The compounds are useful as plant growth modifiers and are distinguished by a high selectivity and a rapid decomposition in the ground.

llite ttes t1 [191 Sehwarze 11] 1*Ja1n. 22, 1974 1 HERBICIDE BASED ONCYANOALKYLAMINOTRIAZINES [75] Inventor: Werner Schwarze, Frankfurt amMain, Germany [73] Assignee: lDeutsche Gold-11nd Silber-ScheideanstaltVormals Roessler, Frankfurt am Main,

Germany Notice: The portion of the term of this patent subsequent toMar. 24, 1987, has been disclaimed.

[22] Filed: Aug. 12, 1971 [21] Appl. N0.: 171,330

Related 1.1.5. Application Data [62] Division of Ser. No. 804,718, March5, 1969, Pat.

Primary Examiner- James 0. Thomas, Jr. Attorney, Agent, or Firm-MichaelS. Striker [57] ABSTRACT A herbicide in whichthe active agent is asubstituted s-triazine of the formula:

wherein X is halogen, alkoxy or alkylmercapto, alkyl in alkoxy andalkylmercapto having one to six carbon atoms; R is wherein n and m arezero or 1 with the provision that only one of n and in may be zero; Rand R are the sameor different and are straight-chain or branchedchainalkyl having from one to four carbon atoms and wherein either R or R mayalso be hydrogen; and R wherein R is hydrogen or straight-chain orbranchedchain lower alkyl.

26 Claims, No Drawings unnmcrnn BASED ON CYANOALKYLNO 1 i" i ICROSS-REFERENCE TO RELATED APPLICATIONS BACKGROUND OF THE INVENTION Theinvention relates to substituted s-triazine compounds and their use asgrowth modifiers for plants and in particular as herbicides. I

s-Triazine compositions are known which in the 2- position either havean azidoor an alkylmercaptogroup or a halogen atom and which in the4-position are substituted by a cyanoalkylamineo group which is attachedto a primary carbon atom. These compositions as disclosed in Belgianpatent Nos. 656,233 and 644,355 do not have any noteworthy herbicidalproperties.

In US. Pat. No. 2,476,547, triazine compounds have also been disclosedwhich contain cyanoalkylamino groups of specific configurations. Anexample, for instance, is the compound 2-chloro-4-amino-6-cyanomethyl-amino-s-triazine.

These compositions are in use as fungicides and insecticides. However,their herbicidal action is so minor that they can destroy leaf funguswithout damaging the plant itself.

It is therefore an object of the present invention to provide forcompounds which can be used for modifying plant growth, and inparticular as herbicides and which are distinguished both by a highselectivity and by a rapid decomposition in the ground.

SUMMARY OF THE INVENTION This object is met by a substituted s-triazineof the formula:

- R -i l wherein X is halogen, alkoxy, or alkylmercapto, alkyl in alkoxyand alkylmercapto having one to six carbon atoms; R is m NI -'(CHI)n(CH7)m N wherein R is hydrogen or straight-chain or branchedchain loweralkyl.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The term lower in connectionwith alkyl groups or the alkyl portion of other groups as used in theabove summaary of the invention and as used in the following descriptionand the claims is to be understood to refer to groups having one to sixcarbon atoms. Preferably,

the groups have one to four carbon atoms.

If X in the above-given formula is halogen, it is preferably chlorine. Afurther preference for X is a lower alkoxy or alkylmercapto group.

If R and R are substituted alkyl or alkenyl groups, the substituents maybe the following groups: OI-I, OR, SR- or CN. R in these groups is againa lower alkyl group.

Starting Materials The starting materials for synthesizing the compoundsof the invention are branched or substituted amines which can be made bymethods described in the literature.

For instance, an amine of the general formula can be made froma-alkylated acrylonitriles by reaction with concentrated aqueous ammoniain an autoclave at temperatures between and C. Specific examples of suchcompounds are the following:

CHaGH--CH2NH2,

colorless liquid, b.p. 7071 C CzH5-CH-CH2NH2,

colorless liquid, btp 81-82 C For instance, if allylcyanide is reactedwith concentrated ammonia (40 percent) in an autoclave for a period of 2hours, 3-amino-butyronitrile is obtained of the following formula:

CHaCH-CH2CN,

ILIHt colorless liquid, b.p. 6869 C In general, compounds of thefollowing formula H3 CH3 nzN-ooimmcu, mg. HQN&-CHECN l t Ila(colorlcss'liquid up. 6668 (1) are obtained likewise by reacting2,2-dialkylated acrylonitrile with ammonia. The necessary acrylonitrilescan be formed by Knoevenagel-condensation of ketones with cyanoaceticacid and subsequent decarboxylation.

Compounds of the type Process of Making the Compounds The compounds ofthe invention can for instance be made as follows: one mole of cyanuricchloride may for instance be reacted with 1 mole of an aminonitrile inthe presence of one mole of a hydrogen halide binding agent such assodium hydroxide, and this may then be followed by reaction with onemole of ammonia or an amine of the general formula NHRR likewise in thepresence of 1 mole of sodium hydroxide. It is also possible first tointroduce the amine of the formula NHRR and subsequently to react withthe aminonitrile.

The thus-obtained 2-chloro-cyanoalkylamino-6-- -(alkyl-)-aminotriazinescan then be converted to the corresponding alkylmercapto compounds byreaction with alkylmercaptans in the presence of an acid receptor. Thecorresponding alkoxy compounds, on the other hand, can be formed byreacting the halogeno triazines with a sodium alcoholate.

UTILITY The compounds of the invention are effective plant growthmodifiers and, in particular, herbicides and are distinguished by a highselectivity and a rapid decomposition in the ground. The compounds maybe used in view of their superior herbicidal properties both before andafter germination. They will affect the plant growth even in very smallconcentrations. Depending on the type of R to R substituents, they canbe used for destroying or selectivity suppressing weeds from anenvironment of cultivated plants, or they may serve to completelydestroy or prevent undesirable plant growth.

The compounds of the invention can also be used for defoliation, forreduction of the fruition, delayed blossoming, etc. They can be usedsingly or in a mixture of different compounds of the invention or in amixture with other type herbicides. They can also be used in admixturewith insecticides, fungicides and fertilizers.

It was surprising that the compounds of the invention had such strongherbicidal action and such high selectivity in spite of the fact thatthey had only a comparatively small survival time in the ground,amounting only to a few months, which is particularly important in caseof rotating crops.

As already indicated, the compounds of the invention, depending on thesubstitutents present, have excellent preemergence or postemergenceactivity or an activity of both types together. In most cases, they arecrystalline compounds and have a high solubility in many organicsolvents. This distinguishes the compounds from many prior-artchloro-bisalkylaminotriazines which have only slight solubility incustomary solvents. The compounds of the invention can therefore be usedvery well for spraying by airplanes in the form of solutions.

Suitable solvents are for instance the following: alcohols, ketones,hydrocarbons, halogenated hydrocarbons such as chloronaphthalene,mineral oils such as diesel fuel, vegetable oils or mixtures of theseseveral materials.

The compounds of the invention can also be used on solid carriermaterials. Examples of such carrier materials are clay, kaolin,diatomaceous earth, bentonite, talcum, finely ground calcium carbonate,charcoal, sawdust, etc.

The effective agents can be mixed in dry form with the carriermaterials. However, they can also be applied to the carrier materials assolutions or emulsions or can be mixed with the carrier materials inthis form subsequent to drying of the mixture.

In order to improve the adherence of the effective agents on the carriermaterials, conventional adhesives may be used such as glue, casein,alginic acid and similar materials.

It is finally also possible to mix the compounds of the invention, ifdesired together with carrier materials, with emulsifying agents andstabilizers, for instance to form a paste or a powder which then may beset up with water to form a suspension.

Suitable cross-linking agents, emulsifiers and stabilizers are anoinic,cationic or non-ionic materials of the conventional types such as Turkeyred oil, fatty acid salts, alkylarylsulfonates, secondary alkylsulfates,resin acid salts, polyethylene ethers of fatty alcohols, fatty acids orfatty amines, quartemary ammonium compounds, ligninsulfone acid,saponin, gelatin, casein. These additives may be used singly or inmixture of different additives.

SPECIFIC EXAMPLES AND TESTS Examples for the compounds of the inventionare listed in the following table I. All of the compounds comply withthe general formula:

making are the following:

EXAMPLE 1 parts of 2-ethylamino-4-(2-cyano-propyl)-amino-6-chloro-triazine, 89'parts bentonite and 1 part of a composition highlydispersed pyrogenically formed silicic acid were Table l -Cominued X R1R" Color and form M.P., C

01 c113 Nnonn-i Mao 137-138 NII-ClIq-(Jll-CN 01 @1115 N11, -do 201-202N1[GII1CHCN c1 0,115 NHCH; ...d0 205-2111 c1 (2H5 Nnclns 188-1811Nn-cm-on-cN c1 c2115 NHCJHri .....do 888ll NHCHaC HCN o1 CH3 NHCzH .do141-143 NH(|JHCH1CN o1 CH3 NHC H1-i .....do 183-184 NH(IJHCH1CN c1 CH3M10111, do -121 NH--CHz-CN c1 CH3 NHCzH1-i ..do 168-169 NH--( JCHzCN 01CH3 NHCH: .....do -157 NH-o-CHPON Nu .1 .1 01.-. CH3 NHCaHs ...do168-169 NH-CHr-J-CN SCHs... CH3 NHCzH Light yellow crystals.. 110-111NH-CHn-iiH-GN sons... CH1 NHCaH1-l .do on NH-CH1-(EH-CN OCH;..* OH; NH:Whlte crystals F. 159, 5-160.5

NH-Om-oH-GN 0CH3.- CH1 NHCH; -....do F. 106

NH-OHr-H-CN 00111.. cm 1111011114 .....do on NH-CHr-JJPL-CN song... ICH3 N11011:, do 011 NH( 1HCHz-CN 001131. CH3 NHCzH ..do 89-90 NH-HCHa--CN SCHa... CH1 NHCzHs Light yellow crysta1s 113 NH-(J-GHa-CN OCHQ.CH3 NHCzHs White crystals 156 NH- CH1CN More specific examples includingthe process of 60 EXAMPLE 2 A mixture of2-isopropylamino-4-(1,1-dimethyl-2-cyanoethyl)-amino-6-methoxy-s-triazine and 90 parts of diatomaceousearth were ground to extreme fineness as in a ball mill. They were thenuseful as a dusting EXAMPLE 3 ground in a ball mill to a fine dust. Thismixture could then 'be used as a dusting powder.

A mixture of 2-isopropylamino-4-(1,1-dimethyl-2- 7cyano-ethyl)-amino-6-methylmercapto-s-triazine, 70 parts of xylene and10 parts of octylphenylpolyglycolethers from di-t-butylphenol and l-12moles ethyleneoxide Hostapal CV) was formed, to which water was thenadded to prepare a stable emulsion.

EXAMPLE 4 25 parts of2-isopropylamino-4-(1-methy1-2-cyanoethyl)-amino-6-chlorotriazine weredissolved in 200 parts of cyclohexanone, 15 parts of xylene and parts ofa substituted naphthalinedisulfonic acid (Nekal BX). After addition ofwater, the mixture resulted in a stable emulsion.

EXAMPLE 5 50 parts of 2-ethylarnino-4-(2-cyano-propyl)-amino-6-methoxy-s-triazine were dissolved in 450 parts of kerosene. Thesolution could immediately be used for spraying.

EXAMPLE 6 67 g of methacrylonitrile and 200 ml of concentrated ammonia(23 percent) were introduced in a 1 liter autoclave. There was furtherintroduced 200 g of ammonia gas and the mass was then rapidly heated to150C. After two hours, it was gradually cooled down, the pressure wasreleased and the homogenous aqueous solution was saturated withpotassium hydroxide. The amine was separated out, dried with potassiumhydroxide and subsequently distilled in a vacuum. l-methyl-2-aminopropionitrile distilled at b.p. 12 70-71C as a colorless liquid.The yield was 61.5 g corresponding to 73.2 percent of the theoreticalyield.

EXAMPLE 7 A mixture of 67 g of allylcyanide and 250 g of an aqueousammonia solution (40 percent) was heated in an autoclave for 3 hours to140-150C upon shaking. After cooling, the aqueous solution was saturatedwith potassium hydroxide, the precipitated amine was separated, driedwith potassium hydroxide and distilled in a vacuum.3-amino-butyronitrile distilled at b.p. 6869C as a colorless liquid. Theyield was 64.7 g. corresponding to 77 percent of the theoretical yield.

EXAMPLE 8 1-cyano-2-methyl-crotonic acid was decarboxylated by a heattreatment to 2,2-dimethyl-acrylonitrile. The crotonic acid had beenobtained by Knoevenagelcondensation from cyanoacetic acid and acetone.

81 g of the nitrile were then heated together with 259 g of a 50 percentaqueous ammonia solution for three hours in an autoclave to atemperature between 140 and 150C. Subsequently, the mass was cooled,then saturated with potassium hydroxide, and the formed amine wasseparated. The amine was dried with potassium hydroxide and distilled ina vacuum. 64.8 g of 2- amino-2,Z-dimethyl-propionitrile distilled atb.p. 68-68C as a colorless liquid which corresponded to 66.3 percent ofthe theoretical yield.

EXAMPLE 9 184.5 g of cyanuric chloride were suspended in 600 ml acetone,then cooled to 0C. 200 g of ice was added. Thereafter, 84 g ofl-methyl-2-amino-propionitrile were added dropwise at 0-2C andsubsequently a solution of 40 g NaOl-l was added in 200 ml H 0. 2 moleof a 50 percent ethylamine solution (180 g) were then added dropwise ata temperature up to 40C. The acetone was removed in a vacuum as soon asthe solution had a neutral reaction (after about one hour) and thesolution was then diluted with water. The white crystals were removed bysuction, washed and dried at 50C in a vacuum. The thus-obtained2-ethylamino-4-( 2- cyano-propyl)-amino-6-chloro-s-triazine had amelting point between 219 and 220C. The yield was 238 g which wasequivalent to 99 percent of the theoretical yield.

EXAMPLE 10 24.05 of the chlorotriazine (1/10 mole) which was obtained inExample 9 was subjected to boiling for eight hours with a solution of6.6 g of sodium methylmercaptide in 200 ml methanol. The solutionsubsequently was concentrated to dryness by evaporation and the residuewas taken up with water. The crystalline product was removed by suctionand dried. There were obtained light-yellow crystals of 2-ethylamino-4-(2-cyano-propyl )-amino-6-methylmercapto-s-triazine with a melting pointbetween 110 and 111C. The yield was 22.5 g corresponding to 85.2 percentof the theoretical yield.

EXAMPLE 1 l 22.65 g of 2-methylamino-4-(2-cyano-propyl)-amino-6-chloro-s-triazine (1 10 mole) were boiled for six hours with asolution of 5.4 g of sodiummethylate in 150 ml methanol. The mixturethen had a neutral reaction. It was evaporated to 1/3 of its initialvolume, whereupon it was poured into water. The precipitated highlyviscous materials resulted in rapid crystallization. After separationand drying, there were obtained 19.9 g of2-methy1amino-4-(2-cyano-propyl)-amino-6- methoxy-s-triazine in the formof white crystals; that is 89.8 percent of the theoretical yield, havinga melting point of 106C.

EXAMPLE 12 55.35 g of cyanuric chloride were suspended in 300 mlacetone, cooled to 0C and, at this temperature, 25.7 g of3-amino-butyronitrile were added upon stirring. A solution of 12 gNaOl-l in 60 ml water was subsequently added. Thereafter, 25.5 g of apercent isopropylamine solution was added dropwise and finally anothersolution of 12 g of NaOl-l in 60 ml 11 0 were added at a temperaturerising up to 45C. As soon as the mixture had a neutral reaction, theacetone was removed in a vacuum, and the residue taken up with water.The white crystals were removed by suction, washed and dried. The formed2-isopropyl-amino-4-( lmethyl-2-cyano-ethyl)-amino-chloro-s-triazine hasa melting point between 183 and 184C. The yield was g corresponding to98 percent of the theoretical yie (1.

EXAMPLE 13 184.5 g of cyamuric chloride were suspended in 600 mlacetone. The mixture was cooled to 0C. Thereafter, 99 g of2,2-dimethyL2-amino-propionitrile were added dropwise at thistemperature and subsequently 200 ml of a S-normal sodium hydroxidesolution were added. The mixture soon had a neutral reaction. At atemperature rising to 40C g of a 50 percent ethylamine solution and 200ml of a 5-N sodium hydroxide solution were added. The neutral solutionwas diluted with two liters of water and the crystals were removed bysuction. After drying, there were obtained 238.5 g of 27.

9 The yield was 93.75 of the theoretical yield. The melting point wasbetween 125 and 127C.

EXAMPLE 14 C. The same process was followed as at B. but with thedistinction that the aqueous dispersion of the effective agent was notapplied to the ground but to the leaves.

The results of the tests will be found in the following Table 11. Theevaluation of the growth was carried out on a scale on which zeroindicated normal growth and 9 total destruction of the plant.

The concentration of the effective agent in the different test serieswas as follows: I

A. kg/ha and 1 kg/ha B. 10 kg/ha, l kg/ha, 0.1 kg/ha C. 10 kg/ha, 1kg/ha, 0.1 kg/ha ha in these statements refers to one hectare equalling2.471 acres. The effective agents of the invention used in these testswere the following, see formula given before Table 1:

EXAMPLE 15 TABLE 11 Tests Compound In order to test the herbicidalactlon of the com- 20 Number X subs ltu nts R pounds of the invention,the following experiments I c1 NHC2H5 CH3 were carried out:

A. Application to the Ground after Seeding: II 01 NHC H 1 CH Variousseeds were embedded by raking in earth a 1 i a which was contained inplastic bowls. The test was car- NH'CH'CmCN ried out in a hot house at atemperature of 21C. The III........... 01 NHCzHs nn earth was watered inthe morning and in the afternoon NmmcmcN and was then treated with adispersion which was ob tained by pouring a solution of the herbicideinto equal IV 00 w H H parts of water. Then normal watering wascontinued, N} 2 3 and the germinating of the plants was checked. TwoNHCHTCHCN weeks after seeding, it was determined whether and to V 0 CH3NHCzH c2135 what extent the plant growth had been suppressed. B.Application to the Ground After Germination: VI 0 CH3 NECHS c2115Various seeds were again placed into the earth by E N raking in ahothouse having an interior temperature of Nil-CH? 21C. Aftergerminating, the aqueous dispersion men- VII S CH3 NHCtHi CH3 tioned atA. of the effective agent of the invention was NH-bH-CHHIN applied tothe ground. After two weeks it was detervml SCHa NHCQH mined whether andto what extent the growth had been NH CH l diminished.

TEST SERIES A Compound kg/ha corn oats ryegrass peas linseed mustardsugar beets 1 20 0 6 8 3 9 9 9 1 o 4 7 l 8 s 8 ll 20 0 7 s 4 9 9 9 1 0 36 2 8 6 7 111 20 o 7 9 4 9 9 9 1 0 3 8 1 s s 9 1v 20 7 9 9 8 9 9 9 1 2 76 3 s 9 9 v 20. 2 6 7 4 9 9 9 1 2 3 3 o 8 7 9 v1 20 5 7 3 9 9 9 9 1 4 4o 7 7 4 7 VII 20 3 7 8 3 9 9 9 1 1 4 6 0 9 4 9 VH1 20 3 5 a 2 9 9 9 1 11 3 1 9 2 s mustard sugar beets linseed TEST SERIES B oats ryegrasskg/ha Compound No.

VIII

mustard sugar beets linseed peas TEST SERIES C oats ryegrass kg/haCompound No.

I I I I I .l

III

VII

VIII

wherein X is halogen, alkoxy or alkylmercapto, alkyl in alkoxy andalkylmercapto having one to six carbon atoms; R is 7 wherein n and m arezero or one with the provision that only one of n and in may be zero; Rand R are the same or different and are straight-chain or branchedchainalkyl having from one to four atoms and wherein either R or R may alsobe hydrogen; and R is l. A herbicide comprising a herbicidally effectiveamount of a substituted s-triazine of the formula What is claimed is:

and R is Nl-lCH 6. The herbicide of claim 1, in which X is Cl and inwhich R is 02115 NHCH;JJHCN and R2 is NHC2H5.

7. The herbicide of claim 1, in which X is C] and in which R is NHCHOH-CN and R is NH is-i. h 7

8. The herbicide of claim 1, in which X is Cl and R is and R is NH 9.The herbicide of claim 1, in which X is Cl and in which R is CH: nacm-cn-cn and R2 is NHC2H5.

13. The herbicide of claim 1, in which X is Cl and in which R is and Ris NHC l-l i.

14. The herbicide of claim 1, in which X is C] and in which R isd1-CHz-CN and R is NHC H 15. The herbicide of claim 1, in which X is Cland in which R is and R is Nl-lC H -i.

16. The herbicide of claim 1, in which X is Cl and in which R is CH:NH--JJIh-C N and R is NHCH 17. The herbicide of claim 1, in which X isC] and in which R is NH-CHz-JJ-CN and R2 1'8 18. The herbicide of claim1, in which X is SCH and in which R is 9 NH-CH1CHON and R is NHC ll 19.The herbicide of claim 1, in which X is SCH and in which R is cii,NH-CHa( JHON and R is NHC H -i. 20. The herbicide of claim 1, in which Xis OCH, and in which R is and R is Ni-ig.

21. The herbicide of claim 1, in which X is OCH and in which R" is and Ris NHCH 22. The herbicide of claim 1, in which X is OCH and in which Ris "as; w

and R is NHC H -i.

23. The herbicide of claim 1, in which X is SCH and in which R is "chiNHCHCH,'UN

and R is NHC l-l 24. The herbicide of claim 1, in which X is OCl-l andin which R is NH-CHCH7-CN and R is NHC H 25. The herbicide of claim 1,in which X is SCI-l and in which R is CH: NH( JCHzCN and R2 is NHC2H,.

26. The herbicide of claim 1, in which X is OCH and in which R is CH: 1NH-JF-CH -CN and R is NHC H :I:

2. The herbicide of claim 1, wherein X is chlorine.
 3. The herbicide ofclaim 1, wherein X is lower alkoxy or lower alkylmercapto.
 4. Theherbicide of claim 1, in which X is Cl and in which R1 is
 5. Theherbicide of claim 1, in which X is Cl and in which R1 is
 6. Theherbicide of claim 1, in which X is Cl and in which R1 is
 7. Theherbicide of claim 1, in which X is Cl and in which R1 is
 8. Theherbicide of claim 1, in which X is Cl and R1 is
 9. The herbicide ofclaim 1, in which X is Cl and in which R1 is
 10. The herbicide of claim1, in which X is Cl and in which R1 is
 11. The herbicide of claim 1, inwhich X is Cl and in which R1 is
 12. The herbicide of claim 1, in whichX is Cl and in which R1 is
 13. The herbicide of claim 1, in which X isCl and in which R1 is
 14. The herbicide of claim 1, in which X is Cl andin which R1 is
 15. The herbicide of claim 1, in which X is Cl and inwhich R1 is
 16. The herbicide of claim 1, in which X is Cl and in whichR1 is
 17. The herbicide of claim 1, in which X is Cl and in which R1 is18. The herbicide of claim 1, in which X is SCH3 and in which R1 is 19.The herbicide of claim 1, in which X is SCH3 and in which R1 is
 20. Theherbicide of claim 1, in which X is OCH3 and in which R1 is
 21. Theherbicide of claim 1, in which X is OCH3 and in which R1 is
 22. Theherbicide of claim 1, in which X is OCH3 and in which R1 is
 23. Theherbicide of claim 1, in which X is SCH3 and in which R1 is
 24. Theherbicide of claim 1, in which X is OCH3 and in which R1 is
 25. Theherbicide of claim 1, in which X is SCH3 and in which R1 is
 26. Theherbicide of claim 1, in which X is OCH3 and in which R1 is